U.S. patent application number 17/570427 was filed with the patent office on 2022-07-21 for solid electrolytic capacitor.
The applicant listed for this patent is KYOCERA AVX Components Corporation. Invention is credited to Junichi Murakami, Jiri Navratil, Hiromasa Noborio, Jan Petrzilek.
Application Number | 20220230815 17/570427 |
Document ID | / |
Family ID | |
Filed Date | 2022-07-21 |
United States Patent
Application |
20220230815 |
Kind Code |
A1 |
Petrzilek; Jan ; et
al. |
July 21, 2022 |
Solid Electrolytic Capacitor
Abstract
A solid electrolytic capacitor comprising a capacitor element,
anode lead extending from a surface of the capacitor element, an
anode termination that is in electrical connection with the anode
lead, a cathode termination that is in electrical connection with
the solid electrolyte, and a casing material that encapsulates the
capacitor element and anode lead is provided. A barrier coating is
disposed on at least a portion of the capacitor element and is in
contact with the casing material. The coating contains a polymeric
material that includes a fluorinated component and a
non-fluorinated component. The polymeric material has a glass
transition temperature of from about 10.degree. C. to about
120.degree. C. and a thermal decomposition temperature of about
200.degree. C. to about 300.degree. C.
Inventors: |
Petrzilek; Jan; (Usti nad
Orlici, CZ) ; Noborio; Hiromasa; (Shiga Pref.,
JP) ; Navratil; Jiri; (Veseli nad Moravou, CZ)
; Murakami; Junichi; (Shiga Pref., JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
KYOCERA AVX Components Corporation |
Fountain Inn |
SC |
US |
|
|
Appl. No.: |
17/570427 |
Filed: |
January 7, 2022 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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63137825 |
Jan 15, 2021 |
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International
Class: |
H01G 9/15 20060101
H01G009/15; H01G 9/012 20060101 H01G009/012; H01G 9/028 20060101
H01G009/028; H01G 9/052 20060101 H01G009/052; H01G 9/08 20060101
H01G009/08 |
Claims
1. A solid electrolytic capacitor comprising: a capacitor element
that contains a sintered porous anode body, a dielectric that
overlies the anode body, and a solid electrolyte that overlies the
dielectric; an anode lead extending from a surface of the capacitor
element; an anode termination that is in electrical connection with
the anode lead and a cathode termination that is in electrical
connection with the solid electrolyte, a casing material that
encapsulates the capacitor element and anode lead; and a barrier
coating that is disposed on at least a portion of the capacitor
element and is in contact with the casing material, wherein the
coating comprises a polymeric material that includes a fluorinated
component and a non-fluorinated component, wherein the polymeric
material has a glass transition temperature of from about
10.degree. C. to about 120.degree. C. and a thermal decomposition
temperature of about 200.degree. C. to about 300.degree. C.
2. The solid electrolytic capacitor of claim 1, wherein the
capacitor exhibits a Moisture Sensitive Level of at least 4 when
tested in accordance with J-STD-020E (December 2014).
3. The solid electrolytic capacitor of claim 1, wherein the
fluorinated component includes a fluorocarbon having a fluoroalkyl
group.
4. The solid electrolytic capacitor of claim 3, wherein the
fluoroalkyl group includes --CF.sub.3, --CF.sub.2CF.sub.3,
--(CF.sub.2).sub.2CF.sub.3, --CF(CF.sub.3).sub.2,
--(CF.sub.2).sub.3CF.sub.3, --CF.sub.2CF(CF.sub.3).sub.2,
--C(CF.sub.3).sub.3, --(CF.sub.2).sub.4CF.sub.3,
--(CF.sub.2).sub.2CF(CF.sub.3).sub.2, --CF.sub.2C(CF.sub.3).sub.3,
--CF(CF.sub.3)CF.sub.2CF.sub.2CF.sub.3, --(CF.sub.2).sub.5CF.sub.3,
--(CF.sub.2).sub.3CF(CF.sub.3).sub.2, or a combination thereof.
5. The solid electrolytic capacitor of claim 3, wherein the
fluorocarbon also contains a (meth)acrylate group.
6. The solid electrolytic capacitor of claim 1, wherein the
fluorinated component includes a fluoroalkyl-substituted
(meth)acrylate.
7. The solid electrolytic capacitor of claim 6, wherein the
fluoroalkyl-substituted (meth)acrylate includes perfluorobutyl
(meth)acrylate, perfluorohexyl (meth)acrylate, perfluoroheptyl
(meth)acrylate, perfluorooctyl (meth)acrylate, perfluorononyl
(meth)acrylate, perfluorodecyl (meth)acrylate, perfluoroundecyl
(meth)acrylate, perfluorododecyl (meth)acrylate, or a combination
thereof.
8. The solid electrolytic capacitor of claim 1, wherein the
fluorinated component and the non-fluorinated component are
monomeric repeating units of a copolymer.
9. The solid electrolytic capacitor of claim 1, wherein the
fluorinated component is a separate material from the
non-fluorinated component.
10. The solid electrolytic capacitor of claim 1, wherein the
non-fluorinated component includes a (meth)acrylate.
11. The solid electrolytic capacitor of claim 10, wherein the
non-fluorinated component includes n-stearyl methacrylate,
n-stearyl acrylate, cyclohexyl methacrylate, behenyl methacrylate,
or a combination thereof.
12. The solid electrolytic capacitor of claim 1, wherein the
barrier coating is in contact with at least a portion of the anode
termination and/or cathode termination.
13. The solid electrolytic capacitor of claim 12, wherein the
barrier coating covers at least a portion of the anode
termination.
14. The solid electrolytic capacitor of claim 1, wherein the
barrier coating covers at least a portion of the anode lead.
15. The solid electrolytic capacitor of claim 1, wherein the
barrier coating covers at least a portion of the surface of the
capacitor element from which the anode lead extends.
16. The solid electrolytic capacitor of claim 1, wherein the casing
material is formed from a resinous matrix.
17. The solid electrolytic capacitor of claim 1, wherein the
capacitor element further comprises a cathode coating that contains
a metal particle layer that overlies the solid electrolyte, wherein
the metal particle layer includes a plurality of conductive metal
particles.
18. The solid electrolytic capacitor of claim 1, wherein the anode
body includes tantalum.
19. The solid electrolytic capacitor of claim 1, wherein the solid
electrolyte includes a conductive polymer.
20. The solid electrolytic capacitor of claim 19, wherein the
conductive polymer has repeating units of the following formula:
##STR00004## wherein, R.sub.7 is a linear or branched, C.sub.1 to
C.sub.18 alkyl radical, C.sub.5 to C.sub.12 cycloalkyl radical,
C.sub.6 to C.sub.14 aryl radical, C.sub.7 to C.sub.18 aralkyl
radical, or a combination thereof; and q is an integer from 0 to
8.
21. The solid electrolytic capacitor of claim 20, wherein the
conductive polymer is poly(3,4-ethylenedioxythiophene).
22. The solid electrolytic capacitor of claim 20, wherein the solid
electrolyte also contains a polymeric counterion.
23. The solid electrolytic capacitor of claim 1, further comprising
an external polymer coating that overlies the solid electrolyte and
contains pre-polymerized conductive polymer particles and a
cross-linking agent.
24. A method for forming the solid electrolytic capacitor of claim
1, the method comprising: disposing a coating formulation on at
least a portion of the anode termination, the coating formulation
containing the polymeric material and a solvent; and removing the
solvent from the coating formulation to form the barrier
coating.
25. The method of claim 24, wherein the solvent includes a
fluorinated hydrocarbon, fluorinated ketone, fluorinated aliphatic
olefin, fluorinated aromatic olefin, or a combination thereof.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] The present application claims filing benefit of U.S.
Provisional Patent Application Ser. No. 63/137,825 having a filing
date of Jan. 15, 2021, which is incorporated herein by reference in
its entirety.
BACKGROUND OF THE INVENTION
[0002] Solid electrolytic capacitors (e.g., tantalum capacitors)
are typically made by pressing a metal powder (e.g., tantalum)
around a metal lead wire, sintering the pressed part, anodizing the
sintered anode, and thereafter applying a solid electrolyte.
Intrinsically conductive polymers are often employed as the solid
electrolyte due to their advantageous low equivalent series
resistance ("ESR") and "non-burning/non-ignition" failure mode. For
example, such electrolytes can be formed through in situ chemical
polymerization of a 3,4-dioxythiophene monomer ("EDOT") in the
presence of a catalyst and dopant. However, conventional capacitors
that employ in situ polymerized polymers tend to have a relatively
high leakage current ("DCL") and fail at high voltages, such as
experienced during a fast switch on or operational current spike.
In an attempt to overcome these issues, dispersions have also been
employed that are formed from a complex of
poly(3,4-ethylenedioxythiophene) and poly(styrene sulfonic acid
("PEDOT:PSS"). While some benefits have been achieved with these
capacitors, problems nevertheless remain. For example, when the
anode is immersed into the conductive polymer dispersion, gaseous
bubbles can form in the polymer layer due to the presence of
moisture from the slurry. The gaseous bubbles effectively become
trapped within the fully applied polymer layer. Therefore, when
they are evaporated during drying, they can actually cause portions
of the polymer layer to tear away and leave behind inhomogeneities
or "blisters" in the surface that reduce the ability of the layer
to adhere to the anode body. Upon exposure to high humidity and/or
temperature environments, these blisters can cause the layer to
delaminate from the anode body, thereby reducing the degree of
electrical contact and resulting in increased leakage current and
ESR.
[0003] To help protect the capacitor from the exterior environment
and provide it with good mechanical stability, the capacitor
element is also encapsulated with a casing material (e.g., epoxy
resin) so that a portion of the anode and cathode terminations
remain exposed for mounting to a surface. Unfortunately, it has
been discovered that high temperatures that are often used during
manufacture of the capacitor (e.g., reflow) can cause residual
moisture to vaporize as steam, which may exit the case with
considerable force and cause micro-cracks to form in the casing
material. These micro-cracks can lead to delamination of the casing
material from the capacitor element and also a rapid deterioration
of the electrical properties. Further, oxygen may also diffuse into
the cathode, further enhancing the degradation of electrical
properties at high temperatures, particularly when the capacitor is
exposed to high temperatures.
[0004] As such, a need exists for an improved solid electrolytic
capacitor that is capable of exhibiting better electrical
performance, particularly at high temperatures.
SUMMARY OF THE INVENTION
[0005] In accordance with one embodiment of the present invention,
a solid electrolytic capacitor is disclosed that comprises a
capacitor element that contains a sintered porous anode body, a
dielectric that overlies the anode body, and a solid electrolyte
that overlies the dielectric; an anode lead extending from a
surface of the capacitor element; an anode termination that is in
electrical connection with the anode lead; a cathode termination
that is in electrical connection with the solid electrolyte; and a
casing material that encapsulates the capacitor element and anode
lead. A barrier coating is disposed on at least a portion of the
capacitor element and is in contact with the casing material. The
coating contains a polymeric material that includes a fluorinated
component and a non-fluorinated component. The polymeric material
has a glass transition temperature of from about 10.degree. C. to
about 120.degree. C. and a thermal decomposition temperature of
about 200.degree. C. to about 300.degree. C.
[0006] Other features and aspects of the present invention are set
forth in greater detail below.
BRIEF DESCRIPTION OF THE DRAWING
[0007] A full and enabling disclosure of the present invention,
including the best mode thereof, directed to one of ordinary skill
in the art, is set forth more particularly in the remainder of the
specification, which makes reference to the appended drawing in
which:
[0008] FIG. 1 is a schematic illustration of one embodiment of a
solid electrolytic capacitor that may be formed in accordance with
the present invention.
[0009] Repeat use of references characters in the present
specification and drawing is intended to represent same or
analogous features or elements of the invention.
DETAILED DESCRIPTION OF REPRESENTATIVE EMBODIMENTS
[0010] It is to be understood by one of ordinary skill in the art
that the present discussion is a description of exemplary
embodiments only, and is not intended as limiting the broader
aspects of the present invention, which broader aspects are
embodied in the exemplary construction.
[0011] Generally speaking, the present invention is directed to a
solid electrolytic capacitor that contains a capacitor element
including a porous anode body, dielectric overlying the anode body,
and solid electrolyte overlying the dielectric. An anode lead
extends from the anode body and is in electrical contact with an
anode termination. A cathode termination is likewise in electrical
contact with the solid electrolyte. Further, a casing material
encapsulates the capacitor element and anode lead and leaves
exposed at least a portion of the anode termination and cathode
termination for external contact. To help minimize the likelihood
of delamination and oxygen diffusion, a barrier coating is also
employed in the capacitor that covers at least a portion of the
capacitor element and is in contact with the casing material.
[0012] The barrier coating contains a polymeric material having a
glass transition temperature of from about 10.degree. C. to about
120.degree. C., in some embodiments from about 20.degree. C. to
about 100.degree. C., in some embodiments from about 30.degree. C.
to about 80.degree. C., and in some embodiments, from about
35.degree. C. to about 50.degree. C., such as determined in
accordance with JIS K 7121:2012 (e.g., at a rate of temperature
increase of 10.degree. C./min). The thermal decomposition
temperature of the polymeric material is also relatively high, such
as from about 200.degree. C. to about 300.degree. C., in some
embodiments from about 210.degree. C. to about 290.degree. C., and
in some embodiments, from about 220.degree. C. to about 280.degree.
C. The thermal decomposition temperature may be determined from a
graph obtained by measuring the change in the mass of the polymeric
material when heated from 50.degree. C. to 450.degree. C. at a rate
of 5.degree. C./min using a differential thermal weight
simultaneous measuring device (e.g., TG/DTA6300, Hitachi). The
thermal decomposition temperature is the temperature of the
extrapolation at the point where the weight begins to decrease and
the point where the slope of the curve is the largest. Without
intending to be limited by theory, it is believed that materials
having such controlled glass transition and thermal decomposition
temperatures may not only act as a barrier to moisture and oxygen,
but they can also help impart the resulting coating with an
enhanced degree of adhesion to to the casing material, which makes
it less likely to delaminate from the capacitor element when
exposed to the high temperatures often experienced during
manufacturing of the capacitor (e.g., reflow).
[0013] Any of a variety of polymeric materials having the desired
properties may be employed in the barrier coating. The polymeric
material, for instance, typically contains at least one fluorinated
component and at least one non-fluorinated component. The
components may be separate materials (e.g., polymers, oligomers, or
non-polymeric compounds) that are simply blended together to form
the polymeric material. Alternatively, the components may be
separate and distinct monomeric repeating units of a single
copolymer. Regardless, the fluorinated component typically
constitutes from about 30 wt. % to about 80 wt. %, and in some
embodiments, from about 40 wt. % to about 75 wt. % of the polymeric
material, and the non-fluorinated component constitutes from about
20 wt. % to about 70 wt. %, and in some embodiments, from about 25
wt. % to about 60 wt. %.
[0014] The fluorinated component may, for instance, be a
fluorocarbon. The fluorocarbon typically contains a fluoroalkyl
group having 1 to 12 carbon atoms, in some embodiments from 1 to 8
carbon atoms, and in some embodiments, from 1 to 6 carbon atoms,
such as --CF.sub.3, --CF.sub.2CF.sub.3, --(CF.sub.2).sub.2CF.sub.3,
--CF(CF.sub.3).sub.2, --(CF.sub.2).sub.3CF.sub.3,
--CF.sub.2CF(CF.sub.3).sub.2, --C(CF.sub.3).sub.3,
--(CF.sub.2).sub.4CF.sub.3, --(CF.sub.2).sub.2CF(CF.sub.3).sub.2,
--CF.sub.2C(CF.sub.3).sub.3,
--CF(CF.sub.3)CF.sub.2CF.sub.2CF.sub.3, --(CF.sub.2).sub.5CF.sub.3,
and --(CF.sub.2).sub.3CF(CF.sub.3).sub.2. The fluorocarbon may also
contain an ethylenically unsaturated group having a carbon chain
length of from 3 to 20 atoms, in some embodiments from 6 to 12
carbon atoms in length, and in some embodiments, from 8 to 10
carbon atoms in length. Examples of such groups may include olefins
(e.g. linear, cyclic, etc.), (meth)acrylates, etc. As used herein,
the term "(meth)acrylate" includes acrylics and methacrylics, as
well as salts or esters thereof, such as acrylates and
methacrylates. The (meth)acrylate may be unsubstituted or
substituted with an alkyl group (e.g., linear olefin, cycloolefin,
etc.). Examples of such (meth)acrylates may include methyl
acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate,
n-butyl acrylate, s-butyl acrylate, 1-butyl acrylate, t-butyl
acrylate, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate,
n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate,
n-octyl acrylate, n-decyl acrylate, n-stearyl acrylate,
methylcyclohexyl acrylate, behenyl acrylate, cyclopentyl acrylate,
cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate,
2-hydroxyethyl methacrylate, n-propyl methacrylate, n-butyl
methacrylate, i-propyl methacrylate, i-butyl methacrylate, n-amyl
methacrylate, n-hexyl methacrylate, i-amyl methacrylate,
s-butyl-methacrylate, t-butyl methacrylate, 2-ethylbutyl
methacrylate, methylcyclohexyl methacrylate, n-octyl methacrylate,
n-decyl methacrylate, n-stearyl methacrylate, cinnamyl
methacrylate, crotyl methacrylate, cyclohexyl methacrylate,
cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, isobornyl
methacrylate, behenyl methacrylate, etc., as well as combinations
thereof. In one particular embodiment, for instance, the
fluorocarbon is a fluoroalkyl-substituted (meth)acrylate, such as
perfluorobutyl (meth)acrylate, perfluorohexyl (meth)acrylate,
perfluoroheptyl (meth)acrylate, perfluorooctyl (meth)acrylate,
perfluorononyl (methacrylate), perfluorodecyl (meth)acrylate,
perfluoroundecyl (meth)acrylate, perfluorododecyl (meth)acrylate,
etc., as well as mixtures thereof.
[0015] As indicated above, the polymeric material also includes a
non-fluorinated component, which may be a separate material (e.g.,
polymer, oligomer, non-polymeric compound) or a separate and
distinct monomeric repeating unit of a copolymer containing both
the fluorinated component and non-fluorinated component. Of course,
in embodiments in which the fluorinated component is not a polymer
or a monomeric repeating unit of a copolymer, it is typically
desired that the non-fluorinated component is a polymer or a
monomeric repeating unit of a copolymer. Regardless, the
non-fluorinated component typically contains an ethylenically
unsaturated group, such as a (meth)acrylate as described above.
[0016] Alkyl-substituted (meth)acrylates are particularly suitable,
such as n-stearyl methacrylate, n-stearyl acrylate, cyclohexyl
methacrylate, behenyl methacrylate, etc. In one particular
embodiment, the polymeric material includes a copolymer that
contains fluorinated monomeric repeating units, such as a
fluoroalkyl-substituted (meth)acrylate as described above, as well
as non-fluorinated monomeric repeating units, such as an
alkyl-substituted (meth)acrylate as described above. Such a polymer
may be produced using any known technique, such as solution
polymerization, suspension polymerization, or emulsion
polymerization. If desired, a polymerization initiator may be
employed to facilitate the polymerization process, such as
2,2'-azobis-2-methylbutyronitrile,
dimethyl-2,2'-azobis-2-methylpropionate,
2,2'-azobisisobutyronitrile, lauroyl peroxide, etc. Specific
examples of such polymerization techniques are described, for
instance, in Japanese Patent Publication Nos. 2020-10080A and
2017-132830A.
[0017] To help aid in its application, the barrier coating may be
initially provided in the form of a coating formulation that
contains the polymeric material in combination with an organic
solvent, which is typically a liquid at room temperature. When
employed, such solvents typically constitute from about 70 wt. % to
about 99.9 wt. %, in some embodiments from about 80 wt. % to about
99.8 wt. %, and in some embodiments, from about 90 wt. % to about
99.5 wt. % of the formulation, while the polymeric material may
constitute from about 0.1 wt. % to about 30 wt. %, in some
embodiments from about 0.2 wt. % to about 20 wt. %, and in some
embodiments, from about 0.5 wt. % to about 10 wt. % of the
solution. The solvent(s) employed will depend in part on the nature
of the polymeric material, but generally include organic alcohols,
hydrocarbon solvents, fluorinated hydrocarbon solvents, etc. For
example, particularly suitable solvents for use with fluoropolymers
include fluorinated hydrocarbon solvents, such as
hydrofluoroethers, fluorinated ketones, fluorinated aliphatic
olefins, fluorinated aromatic olefins (e.g., xylene hexafluoride),
etc. In one particular embodiment, for instance, the coating
formulation may contain a hydrofluoroether having the following
general formula:
(R.sup.1--O).sub.x--R.sup.2
wherein:
[0018] x is 1 or 2;
[0019] one of R.sup.1 and R.sup.2 is a perfluoroaliphatic or
perfluorocyclic group and the other is an aliphatic or a cyclic
hydrocarbon group. For example, R.sup.1 and/or R.sup.2 may include
substituted and nonsubstituted alkyl, aryl, and alkylaryl groups
and their derivatives. Representative examples of suitable
hydrofluoroethers include the following compounds:
C5F.sub.11OC.sub.2H.sub.5, C.sub.3F.sub.7OCH.sub.3,
C.sub.4F.sub.9OCH.sub.3, C.sub.4F.sub.9OCH.sub.5,
C.sub.3F.sub.70CF(CF.sub.3)CF.sub.2OCH.sub.3,
C.sub.4F.sub.9OC.sub.2F.sub.4OC.sub.2F.sub.4OC.sub.2H.sub.5,
C.sub.4F.sub.9O(CF.sub.2).sub.3OCH.sub.3,
C.sub.3F.sub.7CF(OC.sub.2H.sub.5)CF(CF.sub.3).sub.2,
C.sub.2F.sub.5CF(OCH.sub.3)CF(CF.sub.3).sub.2,
C.sub.4F.sub.9OC.sub.2H.sub.4OC.sub.4F.sub.9, etc. Particularly
suitable are ethyl perfluoroisobutyl ether and ethyl perfluorobutyl
ether, both of which are represented by the structure,
C.sub.4F.sub.9OC.sub.2H.sub.5. Once applied, the coating may be
dried, heated, and/or cured to remove any remaining solvent(s) and
leave a coating of the polymeric material at the desired
location.
[0020] Through selective control over the particular nature of the
barrier coating, the resulting capacitor may be resistant to
delamination during manufacturing and can thus exhibit excellent
electrical properties under a variety of conditions. For example,
when subjected to the "Moisture/Reflow Sensitivity Classification
for Non-Hermetic Surface Mount Devices" (J-STD-020E, December 2014)
test, the resulting capacitor can exhibit a Moisture Sensitive
Level of at least 5 (e.g., 5, 4, 3, 2a, 2, or 1), in some cases at
least 4 (e.g., 4, 3, 2a, 2, or 1), in some cases at least 3 (e.g.,
3, 2a, 2, or 1), in some cases at least 2a (e.g., 2a, 2, or 1), in
some cases at least 2 (e.g., 2 or 1), and in some cases equal to 1,
according to the following criteria:
TABLE-US-00001 Moisture Soak Requirements Floor Life Sensitive Time
Temp/Relative Temp/Relative Level (hours) Humidity Time Humidity 1
168 85.degree. C./85% Unlimited .ltoreq.30.degree. C./85% 2 168
85.degree. C./60% 1 year .ltoreq.30.degree. C./60% 2a 696
30.degree. C./60% 4 weeks .ltoreq.30.degree. C./60% 3 192
30.degree. C./60% 168 hours .ltoreq.30.degree. C./60% 4 96
30.degree. C./60% 72 hours .ltoreq.30.degree. C./60% 5 72
30.degree. C./60% 48 hours .ltoreq.30.degree. C./60%
[0021] The capacitor may also exhibit a dry capacitance of about 20
microFarads (.mu.F) or more, in some embodiments about 25 .mu.F or
more, in some embodiments from about 30 to about 100 .mu.F, and in
some embodiments, from about 40 to about 80 .mu.F, measured at a
frequency of 120 Hz at temperature of about 23.degree. C. The
capacitance values can still remain stable even at high
temperatures. For example, the capacitor may exhibit an aged
capacitance value at a temperature of about 23.degree. C. within
the ranges noted above even after being exposed to "high
temperature storage" testing at a temperature of from about
80.degree. C. or more, in some embodiments from about 100.degree.
C. to about 180.degree. C., and in some embodiments, from about
105.degree. C. to about 150.degree. C. (e.g., about 105.degree. C.,
125.degree. C., or 150.degree. C.) fora substantial period of time,
such as for about 100 hours or more, and in some embodiments, from
about 150 hours to about 3,000 hours (e.g., 500, 1,000, 1,500,
2,000, 2,500, or 3,000 hours), and then being allowed to recover
for about 1 to 2 hours. In one embodiment, for example, the
capacitor may exhibit an aged capacitance value (at 23.degree. C.)
within the ranges noted above after being exposed to high
temperature storage testing at a temperature of 150.degree. C. for
3,000 hours (recovery time of from 1 to 2 hours). In this regard,
the ratio of the aged capacitance at 23.degree. C. after being
subjected to "high temperature storage testing" to the initial
capacitance at 23.degree. C. prior to "high temperature storage
testing" may be from about 0.6 to 1, in some embodiments about from
about 0.7 to 1, in some embodiments from about 0.8 to 1, and in
some embodiments, from about 0.9 to 1.
[0022] The capacitor may exhibit other good electrical properties.
For instance, the capacitor may exhibit a relatively low
equivalence series resistance ("ESR"), such as about 200 mohms or
less, in some embodiments about 150 mohms or less, in some
embodiments from about 0.01 to about 100 mohms, and in some
embodiments, from about 0.1 to about 60 mohms, measured at an
operating frequency of 100 kHz and temperature of about 23.degree.
C. Similar to the capacitance values, the aged ESR after "high
temperature storage" testing as described above may also remain
stable and within the ranges noted above. In one embodiment, for
example, the ratio of the aged ESR at 23.degree. C. after being
subjected to "high temperature storage testing" to the initial ESR
at 23.degree. C. prior to "high temperature storage testing" may be
about 10 or less, in some embodiments about 8 or less, in some
embodiments about 5 or less, in some embodiments about from about
0.7 to 4, in some embodiments from about 0.8 to 3, and in some
embodiments, from 1 to about 2.
[0023] The capacitor may also exhibit a DCL of only about 50
microamps (".mu.A") or less, in some embodiments about 40 .mu.A or
less, in some embodiments about 30 .mu.A or less, in some
embodiments about 20 .mu.A or less, in some embodiments about 10
.mu.A or less, in some embodiments from about 9 .mu.A or less, and
in some embodiments, from about 0.01 to about 8 .mu.A at a
temperature of about 23.degree. C. after being subjected to an
applied voltage (e.g., rated voltage or a multiple of the rated
voltage, such as 1.1.times. rated voltage) for a period of time of
about 60 seconds. Notably, the low DCL values can still remain
stable even at temperatures. For example, the capacitor may exhibit
a low DCL within the ranges noted above after being exposed to high
temperatures, such as of from about 80.degree. C. to about
150.degree. C. (e.g., about 85.degree. C.) for a substantial period
of time, such as for about 100 hours or more, and in some
embodiments, from about 120 hours to about 1,500 hours (e.g., 120,
250, 500, 1,000, or 1,500 hours), and then being allowed to recover
for about 1 to 2 hours. In one embodiment, for example, the
capacitor may exhibit an aged
[0024] DCL value (at 23.degree. C.) within the ranges noted above
after being exposed to testing at a temperature of 85.degree. C.
for 1,500 hours (recovery time of from 1 to 2 hours). In this
regard, the ratio of the aged DCL at 23.degree. C. after being
subjected to "high temperature testing" to the initial DCL at
23.degree. C. prior to "high temperature testing" may be about 10
or less, in some embodiments about 5 or less, in some embodiments
about 2 or less, in some embodiments about 1 or less, in some
embodiments from about 0.05 to about 0.8, and in some embodiments,
from about 0.1 to about 0.5.
[0025] The DCL may also remain stable after being exposed to "high
humidity testing" at a high relative humidity level (without or
without the high temperatures indicated above), such as about 40%
or more, in some embodiments about 45% or more, in some embodiments
about 50% or more, and in some embodiments, about 70% or more
(e.g., about 85% to 100%) for a substantial period of time as noted
above. Relative humidity may, for instance, be determined in
accordance with ASTM E337-02, Method A (2007). For example, the
capacitor may exhibit an aged DCL value (at 23.degree. C.) within
the ranges noted above after being exposed to a humidity level of
85% and temperature of 85.degree. C. for a substantial period of
time, such as for about 100 hours or more, and in some embodiments,
from about 120 hours to about 1,500 hours (e.g., 120, 250, 500,
1,000, or 1,500 hours), and then being allowed to recover for about
1 to 2 hours. For example, the ratio of the aged
[0026] DCL (23.degree. C.) of the capacitor after being exposed to
a high humidity level (e.g., about 85%) and high temperature (e.g.,
about 85.degree. C.) for 1,500 hours (recovery time of 1 to 2 hrs)
to the initial DCL prior to such testing may be about 10 or less,
in some embodiments about 5 or less, in some embodiments about 2 or
less, in some embodiments about 1 or less, in some embodiments from
about 0.05 to about 0.8, and in some embodiments, from about 0.1 to
about 0.5.
[0027] Various embodiments of the capacitor will now be described
in more detail.
I. Capacitor Element
[0028] A. Anode Body
[0029] The capacitor element includes an anode that contains a
dielectric formed on a sintered porous body. The porous anode body
may be formed from a powder that contains a valve metal (i.e.,
metal that is capable of oxidation) or valve metal-based compound,
such as tantalum, niobium, aluminum, hafnium, titanium, alloys
thereof, oxides thereof, nitrides thereof, and so forth. The powder
is typically formed from a reduction process in which a tantalum
salt (e.g., potassium fluorotantalate (K.sub.2TaF.sub.7), sodium
fluorotantalate (Na.sub.2TaF.sub.7), tantalum pentachloride
(TaCl.sub.5), etc.) is reacted with a reducing agent. The reducing
agent may be provided in the form of a liquid, gas (e.g.,
hydrogen), or solid, such as a metal (e.g., sodium), metal alloy,
or metal salt. In one embodiment, for instance, a tantalum salt
(e.g., TaCl.sub.5) may be heated at a temperature of from about
900.degree. C. to about 2,000.degree. C., in some embodiments from
about 1,000.degree. C. to about 1,800.degree. C., and in some
embodiments, from about 1,100.degree. C. to about 1,600.degree. C.,
to form a vapor that can be reduced in the presence of a gaseous
reducing agent (e.g., hydrogen). Additional details of such a
reduction reaction may be described in WO 2014/199480 to Maeshima,
et al. After the reduction, the product may be cooled, crushed, and
washed to form a powder.
[0030] The specific charge of the powder typically varies from
about 2,000 to about 600,000 microFarads*Volts per gram
(".mu.F*V/g") depending on the desired application. For instance,
in certain embodiments, a high charge powder may be employed that
has a specific charge of from about 100,000 to about 550,000
.mu.F*V/g, in some embodiments from about 120,000 to about 500,000
.mu.F*V/g, and in some embodiments, from about 150,000 to about
400,000 .mu.F*V/g. In other embodiments, a low charge powder may be
employed that has a specific charge of from about 2,000 to about
100,000 .mu.F*V/g, in some embodiments from about 5,000 to about
80,000 .mu.F*V/g, and in some embodiments, from about 10,000 to
about 70,000 .mu.F*V/g. As is known in the art, the specific charge
may be determined by multiplying capacitance by the anodizing
voltage employed, and then dividing this product by the weight of
the anodized electrode body.
[0031] The powder may be a free-flowing, finely divided powder that
contains primary particles. The primary particles of the powder
generally have a median size (D50) of from about 5 to about 500
nanometers, in some embodiments from about 10 to about 400
nanometers, and in some embodiments, from about 20 to about 250
nanometers, such as determined using a laser particle size
distribution analyzer made by BECKMAN COULTER Corporation (e.g.,
LS-230), optionally after subjecting the particles to an ultrasonic
wave vibration of 70 seconds. The primary particles typically have
a three-dimensional granular shape (e.g., nodular or angular). Such
particles typically have a relatively low "aspect ratio", which is
the average diameter or width of the particles divided by the
average thickness ("D/T"). For example, the aspect ratio of the
particles may be about 4 or less, in some embodiments about 3 or
less, and in some embodiments, from about 1 to about 2. In addition
to primary particles, the powder may also contain other types of
particles, such as secondary particles formed by aggregating (or
agglomerating) the primary particles. Such secondary particles may
have a median size (D50) of from about 1 to about 500 micrometers,
and in some embodiments, from about 10 to about 250
micrometers.
[0032] Agglomeration of the particles may occur by heating the
particles and/or through the use of a binder. For example,
agglomeration may occur at a temperature of from about 0.degree. C.
to about 40.degree. C., in some embodiments from about 5.degree. C.
to about 35.degree. C., and in some embodiments, from about
15.degree. C. to about 30.degree. C. Suitable binders may likewise
include, for instance, poly(vinyl butyral); poly(vinyl acetate);
poly(vinyl alcohol); poly(vinyl pyrollidone); cellulosic polymers,
such as carboxymethylcellulose, methyl cellulose, ethyl cellulose,
hydroxyethyl cellulose, and methylhydroxyethyl cellulose; atactic
polypropylene, polyethylene; polyethylene glycol (e.g., Carbowax
from Dow Chemical Co.); polystyrene, poly(butadiene/styrene);
polyamides, polyimides, and polyacrylamides, high molecular weight
polyethers; copolymers of ethylene oxide and propylene oxide;
fluoropolymers, such as polytetrafluoroethylene, polyvinylidene
fluoride, and fluoro-olefin copolymers; acrylic polymers, such as
sodium polyacrylate, poly(lower alkyl acrylates), poly(lower alkyl
methacrylates) and copolymers of lower alkyl acrylates and
methacrylates; and fatty acids and waxes, such as stearic and other
soapy fatty acids, vegetable wax, microwaxes (purified paraffins),
etc.
[0033] The resulting powder may be compacted to form a pellet using
any conventional powder press device. For example, a press mold may
be employed that is a single station compaction press containing a
die and one or multiple punches. Alternatively, anvil-type
compaction press molds may be used that use only a die and single
lower punch. Single station compaction press molds are available in
several basic types, such as cam, toggle/knuckle and
eccentric/crank presses with varying capabilities, such as single
action, double action, floating die, movable platen, opposed ram,
screw, impact, hot pressing, coining or sizing. The powder may be
compacted around an anode lead, which may be in the form of a wire,
sheet, etc. The lead may extend in a longitudinal direction from
the anode body and may be formed from any electrically conductive
material, such as tantalum, niobium, aluminum, hafnium, titanium,
etc., as well as electrically conductive oxides and/or nitrides of
thereof. Connection of the lead may also be accomplished using
other known techniques, such as by welding the lead to the body or
embedding it within the anode body during formation (e.g., prior to
compaction and/or sintering).
[0034] Any binder may be removed after pressing by heating the
pellet under vacuum at a certain temperature (e.g., from about
150.degree. C. to about 500.degree. C.) for several minutes.
Alternatively, the binder may also be removed by contacting the
pellet with an aqueous solution, such as described in U.S. Pat. No.
6,197,252 to Bishop, et al. Thereafter, the pellet is sintered to
form a porous, integral mass. The pellet is typically sintered at a
temperature of from about 700.degree. C. to about 1800.degree. C.,
in some embodiments from about 800.degree. C. to about 1700.degree.
C., and in some embodiments, from about 900.degree. C. to about
1400.degree. C., for a time of from about 5 minutes to about 100
minutes, and in some embodiments, from about 8 minutes to about 15
minutes. This may occur in one or more steps. If desired, sintering
may occur in an atmosphere that limits the transfer of oxygen atoms
to the anode. For example, sintering may occur in a reducing
atmosphere, such as in a vacuum, inert gas, hydrogen, etc. The
reducing atmosphere may be at a pressure of from about 10 Torr to
about 2000 Torr, in some embodiments from about 100 Torr to about
1000 Torr, and in some embodiments, from about 100 Torr to about
930 Torr. Mixtures of hydrogen and other gases (e.g., argon or
nitrogen) may also be employed.
[0035] B. Dielectric
[0036] The anode is also coated with a dielectric. The dielectric
may be formed by anodically oxidizing ("anodizing") the sintered
anode so that a dielectric layer is formed over and/or within the
anode. For example, a tantalum (Ta) anode may be anodized to
tantalum pentoxide (Ta.sub.2O.sub.5). Typically, anodization is
performed by initially applying a solution to the anode, such as by
dipping anode into the electrolyte. A solvent is generally
employed, such as water (e.g., deionized water). To enhance ionic
conductivity, a compound may be employed that is capable of
dissociating in the solvent to form ions. Examples of such
compounds include, for instance, acids, such as described below
with respect to the electrolyte. For example, an acid (e.g.,
phosphoric acid) may constitute from about 0.01 wt. % to about 5
wt. %, in some embodiments from about 0.05 wt. % to about 0.8 wt.
%, and in some embodiments, from about 0.1 wt. % to about 0.5 wt. %
of the anodizing solution. If desired, blends of acids may also be
employed.
[0037] A current is passed through the anodizing solution to form
the dielectric layer. The value of the formation voltage manages
the thickness of the dielectric layer. For example, the power
supply may be initially set up at a galvanostatic mode until the
required voltage is reached. Thereafter, the power supply may be
switched to a potentiostatic mode to ensure that the desired
dielectric thickness is formed over the entire surface of the
anode. Of course, other known methods may also be employed, such as
pulse or step potentiostatic methods. The voltage at which anodic
oxidation occurs typically ranges from about 4 to about 250 V, and
in some embodiments, from about 5 to about 200 V, and in some
embodiments, from about 10 to about 150 V. During oxidation, the
anodizing solution can be kept at an elevated temperature, such as
about 30.degree. C. or more, in some embodiments from about
40.degree. C. to about 200.degree. C., and in some embodiments,
from about 50.degree. C. to about 100.degree. C. Anodic oxidation
can also be done at ambient temperature or lower. The resulting
dielectric layer may be formed on a surface of the anode and within
its pores.
[0038] Although not required, in certain embodiments, the
dielectric layer may possess a differential thickness throughout
the anode in that it possesses a first portion that overlies an
external surface of the anode and a second portion that overlies an
interior surface of the anode. In such embodiments, the first
portion is selectively formed so that its thickness is greater than
that of the second portion. It should be understood, however, that
the thickness of the dielectric layer need not be uniform within a
particular region. Certain portions of the dielectric layer
adjacent to the external surface may, for example, actually be
thinner than certain portions of the layer at the interior surface,
and vice versa. Nevertheless, the dielectric layer may be formed
such that at least a portion of the layer at the external surface
has a greater thickness than at least a portion at the interior
surface. Although the exact difference in these thicknesses may
vary depending on the particular application, the ratio of the
thickness of the first portion to the thickness of the second
portion is typically from about 1.2 to about 40, in some
embodiments from about 1.5 to about 25, and in some embodiments,
from about 2 to about 20.
[0039] To form a dielectric layer having a differential thickness,
a multi-stage process is generally employed. In each stage of the
process, the sintered anode is anodically oxidized ("anodized") to
form a dielectric layer (e.g., tantalum pentoxide). During the
first stage of anodization, a relatively small forming voltage is
typically employed to ensure that the desired dielectric thickness
is achieved for the inner region, such as forming voltages ranging
from about 1 to about 90 volts, in some embodiments from about 2 to
about 50 volts, and in some embodiments, from about 5 to about 20
volts. Thereafter, the sintered body may then be anodically
oxidized in a second stage of the process to increase the thickness
of the dielectric to the desired level. This is generally
accomplished by anodizing in an electrolyte at a higher voltage
than employed during the first stage, such as at forming voltages
ranging from about 50 to about 350 volts, in some embodiments from
about 60 to about 300 volts, and in some embodiments, from about 70
to about 200 volts. During the first and/or second stages, the
electrolyte may be kept at a temperature within the range of from
about 15.degree. C. to about 95.degree. C., in some embodiments
from about 20.degree. C. to about 90.degree. C., and in some
embodiments, from about 25.degree. C. to about 85.degree. C.
[0040] The electrolytes employed during the first and second stages
of the anodization process may be the same or different. Typically,
however, it is desired to employ different solutions to help better
facilitate the attainment of a higher thickness at the outer
portions of the dielectric layer. For example, it may be desired
that the electrolyte employed in the second stage has a lower ionic
conductivity than the electrolyte employed in the first stage to
prevent a significant amount of oxide film from forming on the
internal surface of anode. In this regard, the electrolyte employed
during the first stage may contain an acidic compound, such as
nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid,
boric acid, boronic acid, etc. Such an electrolyte may have an
electrical conductivity of from about 0.1 to about 100 mS/cm, in
some embodiments from about 0.2 to about 20 mS/cm, and in some
embodiments, from about 1 to about 10 mS/cm, determined at a
temperature of 25.degree. C. The electrolyte employed during the
second stage typically contains a salt of a weak acid so that the
hydronium ion concentration increases in the pores as a result of
charge passage therein. Ion transport or diffusion is such that the
weak acid anion moves into the pores as necessary to balance the
electrical charges. As a result, the concentration of the principal
conducting species (hydronium ion) is reduced in the establishment
of equilibrium between the hydronium ion, acid anion, and
undissociated acid, thus forms a poorer-conducting species. The
reduction in the concentration of the conducting species results in
a relatively high voltage drop in the electrolyte, which hinders
further anodization in the interior while a thicker oxide layer, is
being built up on the outside to a higher formation voltage in the
region of continued high conductivity. Suitable weak acid salts may
include, for instance, ammonium or alkali metal salts (e.g.,
sodium, potassium, etc.) of boric acid, boronic acid, acetic acid,
oxalic acid, lactic acid, adipic acid, etc. Particularly suitable
salts include sodium tetraborate and ammonium pentaborate. Such
electrolytes typically have an electrical conductivity of from
about 0.1 to about 20 mS/cm, in some embodiments from about 0.5 to
about 10 mS/cm, and in some embodiments, from about 1 to about 5
mS/cm, determined at a temperature of 25.degree. C.
[0041] If desired, each stage of anodization may be repeated for
one or more cycles to achieve the desired dielectric thickness.
Furthermore, the anode may also be rinsed or washed with another
solvent (e.g., water) after the first and/or second stages to
remove the electrolyte.
[0042] C. Solid Electrolyte
[0043] A solid electrolyte overlies the dielectric and generally
functions as the cathode for the capacitor. The solid electrolyte
may include materials as is known in the art, such as conductive
polymers (e.g., polypyrroles, polythiophenes, polyanilines, etc.),
manganese dioxide, and so forth. In one embodiment, for example,
the solid electrolyte contains one or more layers containing
extrinsically and/or intrinsically conductive polymer particles.
One benefit of employing such particles is that they can minimize
the presence of ionic species (e.g., Fe.sup.2+ or Fe.sup.3+)
produced during conventional in situ polymerization processes,
which can cause dielectric breakdown under high electric field due
to ionic migration. Thus, by applying the conductive polymer as
pre-polymerized particles rather through in situ polymerization,
the resulting capacitor may exhibit a relatively high "breakdown
voltage." If desired, the solid electrolyte may be formed from one
or multiple layers. When multiple layers are employed, it is
possible that one or more of the layers includes a conductive
polymer formed by in situ polymerization. However, when it is
desired to achieve very high breakdown voltages, the solid
electrolyte may desirably be formed primarily from the conductive
particles described above, such that it is generally free of
conductive polymers formed via in situ polymerization. Regardless
of the number of layers employed, the resulting solid electrolyte
typically has a total a thickness of from about 1 micrometer
(.mu.m) to about 200 .mu.m, in some embodiments from about 2 .mu.m
to about 50 .mu.m, and in some embodiments, from about 5 .mu.m to
about 30 .mu.m.
[0044] Thiophene polymers are particularly suitable for use in the
solid electrolyte. In certain embodiments, for instance, an
"extrinsically" conductive thiophene polymer may be employed in the
solid electrolyte that has repeating units of the following formula
(I):
##STR00001##
wherein,
[0045] R.sub.7 is a linear or branched, C.sub.1 to C.sub.18 alkyl
radical (e.g., methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or
tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,
1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,
2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl,
n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl,
n-hexadecyl, n-octadecyl, etc.); C.sub.5 to C.sub.12 cycloalkyl
radical (e.g., cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,
cyclononyl, cyclodecyl, etc.); C.sub.6 to C.sub.14 aryl radical
(e.g., phenyl, naphthyl, etc.); C.sub.7 to C.sub.18 aralkyl radical
(e.g., benzyl, o-, m-, p-tolyl, 2,3-, 2,4-, 2,5-, 2-6, 3-4-,
3,5-xylyl, mesityl, etc.); and
[0046] q is an integer from 0 to 8, in some embodiments, from 0 to
2, and in one embodiment, 0. In one particular embodiment, "q" is 0
and the polymer is poly(3,4-ethylenedioxythiophene). One
commercially suitable example of a monomer suitable for forming
such a polymer is 3,4-ethylenedioxthiophene, which is available
from Heraeus under the designation Clevios.TM. M.
[0047] The polymers of formula (I) are generally considered to be
"extrinsically" conductive to the extent that they typically
require the presence of a separate counterion that is not
covalently bound to the polymer. The counterion may be a monomeric
or polymeric anion that counteracts the charge of the conductive
polymer. Polymeric anions can, for example, be anions of polymeric
carboxylic acids (e.g., polyacrylic acids, polymethacrylic acid,
polymaleic acids, etc.); polymeric sulfonic acids (e.g.,
polystyrene sulfonic acids ("PSS"), polyvinyl sulfonic acids,
etc.); and so forth. The acids may also be copolymers, such as
copolymers of vinyl carboxylic and vinyl sulfonic acids with other
polymerizable monomers, such as acrylic acid esters and styrene.
Likewise, suitable monomeric anions include, for example, anions of
C.sub.1 to C.sub.20 alkane sulfonic acids (e.g., dodecane sulfonic
acid); aliphatic perfluorosulfonic acids (e.g., trifluoromethane
sulfonic acid, perfluorobutane sulfonic acid or perfluorooctane
sulfonic acid); aliphatic C.sub.1 to C.sub.20 carboxylic acids
(e.g., 2-ethyl-hexylcarboxylic acid); aliphatic perfluorocarboxylic
acids (e.g., trifluoroacetic acid or perfluorooctanoic acid);
aromatic sulfonic acids optionally substituted by C.sub.1 to
C.sub.20 alkyl groups (e.g., benzene sulfonic acid, o-toluene
sulfonic acid, p-toluene sulfonic acid or dodecylbenzene sulfonic
acid); cycloalkane sulfonic acids (e.g., camphor sulfonic acid or
tetrafluoroborates, hexafluorophosphates, perchlorates,
hexafluoroantimonates, hexafluoroarsenates or
hexachloroantimonates), and so forth. Particularly suitable
counteranions are polymeric anions, such as a polymeric carboxylic
or sulfonic acid (e.g., polystyrene sulfonic acid ("PSS")). The
molecular weight of such polymeric anions typically ranges from
about 1,000 to about 2,000,000, and in some embodiments, from about
2,000 to about 500,000.
[0048] Intrinsically conductive polymers may also be employed that
have a positive charge located on the main chain that is at least
partially compensated by anions covalently bound to the polymer.
For example, one example of a suitable intrinsically conductive
thiophene polymer may have repeating units of the following formula
(II):
##STR00002##
wherein,
[0049] R is (CH.sub.2).sub.a--O--(CH.sub.2).sub.b-L, where L is a
bond or HC([CH.sub.2].sub.cH),
[0050] a is from 0 to 10, in some embodiments from 0 to 6, and in
some embodiments, from 1 to 4 (e.g., 1);
[0051] b is from 1 to 18, in some embodiments from 1 to 10, and in
some embodiments, from 2 to 6 (e.g., 2, 3, 4, or 5);
[0052] c is from 0 to 10, in some embodiments from 0 to 6, and in
some embodiments, from 1 to 4 (e.g., 1);
[0053] Z is an anion, such as SO.sub.3.sup.-, C(O)O.sup.-,
BF.sub.4.sup.-, CF.sub.3SO.sub.3.sup.-, SbF.sub.6.sup.-,
N(SO.sub.2CF.sub.3).sub.2.sup.-, C.sub.4H.sub.3O.sub.4.sup.-,
ClO.sub.4.sup.-, etc.;
[0054] X is a cation, such as hydrogen, an alkali metal (e.g.,
lithium, sodium, rubidium, cesium, or potassium), ammonium,
etc.
[0055] In one particular embodiment, Z in formula (II) is a
sulfonate ion such that the intrinsically conductive polymer
contains repeating units of the following formula (III):
##STR00003##
[0056] wherein, R and X are defined above. In formula (II) or
(III), a is preferably 1 and b is preferably 3 or 4. Likewise, X is
preferably sodium or potassium.
[0057] If desired, the polymer may be a copolymer that contains
other types of repeating units. In such embodiments, the repeating
units of formula (II) typically constitute about 50 mol. % or more,
in some embodiments from about 75 mol. % to about 99 mol. %, and in
some embodiments, from about 85 mol. % to about 95 mol. % of the
total amount of repeating units in the copolymer. Of course, the
polymer may also be a homopolymer to the extent that it contains
100 mol. % of the repeating units of formula (II). Specific
examples of such homopolymers include
poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butane-sulpho-
nic acid, salt) and
poly(4-(2,3-dihydrothieno-[3,4-b][l,4]dioxin-2-ylmethoxy)-l-propanesulpho-
nic acid, salt).
[0058] Regardless of the particular nature of the polymer, the
resulting conductive polymer particles typically have an average
size (e.g., diameter) of from about 1 to about 80 nanometers, in
some embodiments from about 2 to about 70 nanometers, and in some
embodiments, from about 3 to about 60 nanometers. The diameter of
the particles may be determined using known techniques, such as by
ultracentrifuge, laser diffraction, etc. The shape of the particles
may likewise vary. In one particular embodiment, for instance, the
particles are spherical in shape. However, it should be understood
that other shapes are also contemplated by the present invention,
such as plates, rods, discs, bars, tubes, irregular shapes,
etc.
[0059] Although not necessarily required, the conductive polymer
particles may be applied in the form of a dispersion. The
concentration of the conductive polymer in the dispersion may vary
depending on the desired viscosity of the dispersion and the
particular manner in which the dispersion is to be applied to the
capacitor element. Typically, however, the polymer constitutes from
about 0.1 to about 10 wt. %, in some embodiments from about 0.4 to
about 5 wt. %, and in some embodiments, from about 0.5 to about 4
wt. % of the dispersion. The dispersion may also contain one or
more components to enhance the overall properties of the resulting
solid electrolyte. For example, the dispersion may contain a binder
to further enhance the adhesive nature of the polymeric layer and
also increase the stability of the particles within the dispersion.
The binder may be organic in nature, such as polyvinyl alcohols,
polyvinyl pyrrolidones, polyvinyl chlorides, polyvinyl acetates,
polyvinyl butyrates, polyacrylic acid esters, polyacrylic acid
amides, polymethacrylic acid esters, polymethacrylic acid amides,
polyacrylonitriles, styrene/acrylic acid ester, vinyl
acetate/acrylic acid ester and ethylene/vinyl acetate copolymers,
polybutadienes, polyisoprenes, polystyrenes, polyethers,
polyesters, polycarbonates, polyurethanes, polyamides, polyimides,
polysulfones, melamine formaldehyde resins, epoxide resins,
silicone resins or celluloses. Crosslinking agents may also be
employed to enhance the adhesion capacity of the binders. Such
crosslinking agents may include, for instance, melamine compounds,
masked isocyanates or crosslinkable polymers, such as
polyurethanes, polyacrylates or polyolefins, and subsequent
crosslinking. Dispersion agents may also be employed to facilitate
the ability to apply the layer to the anode. Suitable dispersion
agents include solvents, such as aliphatic alcohols (e.g.,
methanol, ethanol, i-propanol and butanol), aliphatic ketones
(e.g., acetone and methyl ethyl ketones), aliphatic carboxylic acid
esters (e.g., ethyl acetate and butyl acetate), aromatic
hydrocarbons (e.g., toluene and xylene), aliphatic hydrocarbons
(e.g., hexane, heptane and cyclohexane), chlorinated hydrocarbons
(e.g., dichloromethane and dichloroethane), aliphatic nitriles
(e.g., acetonitrile), aliphatic sulfoxides and sulfones (e.g.,
dimethyl sulfoxide and sulfolane), aliphatic carboxylic acid amides
(e.g., methylacetamide, dimethylacetamide and dimethylformamide),
aliphatic and araliphatic ethers (e.g., diethylether and anisole),
water, and mixtures of any of the foregoing solvents. A
particularly suitable dispersion agent is water.
[0060] In addition to those mentioned above, still other
ingredients may also be used in the dispersion. For example,
conventional fillers may be used that have a size of from about 10
nanometers to about 100 micrometers, in some embodiments from about
50 nanometers to about 50 micrometers, and in some embodiments,
from about 100 nanometers to about 30 micrometers. Examples of such
fillers include calcium carbonate, silicates, silica, calcium or
barium sulfate, aluminum hydroxide, glass fibers or bulbs, wood
flour, cellulose powder carbon black, electrically conductive
polymers, etc. The fillers may be introduced into the dispersion in
powder form, but may also be present in another form, such as
fibers.
[0061] Surface-active substances may also be employed in the
dispersion, such as ionic or non-ionic surfactants. Furthermore,
adhesives may be employed, such as organofunctional silanes or
their hydrolysates, for example 3-glycidoxypropyltrialkoxysilane,
3-aminopropyl-triethoxysilane, 3-mercaptopropyl-trimethoxysilane,
3-metacryloxypropyltrimethoxysilane, vinyltrimethoxysilane or
octyltriethoxysilane. The dispersion may also contain additives
that increase conductivity, such as ether group-containing
compounds (e.g., tetrahydrofuran), lactone group-containing
compounds (e.g., .gamma.-butyrolactone or .gamma.-valerolactone),
amide or lactam group-containing compounds (e.g., caprolactam,
N-methylcaprolactam, N,N-dimethylacetamide, N-methylacetamide,
N,N-dimethylformamide (DMF), N-methylformamide,
N-methylformanilide, N-methylpyrrolidone (NMP), N-octylpyrrolidone,
or pyrrolidone), sulfones and sulfoxides (e.g., sulfolane
(tetramethylenesulfone) or dimethylsulfoxide (DMSO)), sugar or
sugar derivatives (e.g., saccharose, glucose, fructose, or
lactose), sugar alcohols (e.g., sorbitol or mannitol), furan
derivatives (e.g., 2-furancarboxylic acid or 3-furancarboxylic
acid), an alcohols (e.g., ethylene glycol, glycerol, di- or
triethylene glycol).
[0062] The dispersion may be applied using a variety of known
techniques, such as by spin coating, impregnation, pouring,
dropwise application, injection, spraying, doctor blading,
brushing, printing (e.g., ink-jet, screen, or pad printing), or
dipping. The viscosity of the dispersion is typically from about
0.1 to about 100,000 meas (measured at a shear rate of 100
s.sup.-1), in some embodiments from about 1 to about 10,000 meas,
in some embodiments from about 10 to about 1,500 meas, and in some
embodiments, from about 100 to about 1000 meas. [0063] i. Inner
Layers
[0064] The solid electrolyte is generally formed from one or more
"inner" conductive polymer layers. The term "inner" in this context
refers to one or more layers that overly the dielectric, whether
directly or via another layer (e.g., pre-coat layer). One or
multiple inner layers may be employed. For example, the solid
electrolyte typically contains from 2 to 30, in some embodiments
from 4 to 20, and in some embodiments, from about 5 to 15 inner
layers (e.g., 10 layers). The inner layer(s) may, for example,
contain intrinsically and/or extrinsically conductive polymer
particles such as described above. For instance, such particles may
constitute about 50 wt. % or more, in some embodiments about 70 wt.
% or more, and in some embodiments, about 90 wt. % or more (e.g.,
100 wt. %) of the inner layer(s). In alternative embodiments, the
inner layer(s) may contain an in-situ polymerized conductive
polymer. In such embodiments, the in-situ polymerized polymers may
constitute about 50 wt. % or more, in some embodiments about 70 wt.
% or more, and in some embodiments, about 90 wt. % or more (e.g.,
100 wt. %) of the inner layer(s). [0065] ii. Outer Layers
[0066] The solid electrolyte may also contain one or more optional
"outer" conductive polymer layers that overly the inner layer(s)
and are formed from a different material. For example, the outer
layer(s) may contain extrinsically conductive polymer particles. In
one particular embodiment, the outer layer(s) are formed primarily
from such extrinsically conductive polymer particles in that they
constitute about 50 wt. % or more, in some embodiments about 70 wt.
% or more, and in some embodiments, about 90 wt. % or more (e.g.,
100 wt. %) of a respective outer layer. One or multiple outer
layers may be employed. For example, the solid electrolyte may
contain from 2 to 30, in some embodiments from 4 to 20, and in some
embodiments, from about 5 to 15 outer layers, each of which may
optionally be formed from a dispersion of the extrinsically
conductive polymer particles.
[0067] D. External Polymer Coating
[0068] An external polymer coating may also overly the solid
electrolyte. The external polymer coating may contain one or more
layers formed from pre-polymerized conductive polymer particles
such as described above (e.g., dispersion of extrinsically
conductive polymer particles). The external coating may be able to
further penetrate into the edge region of the capacitor body to
increase the adhesion to the dielectric and result in a more
mechanically robust part, which may reduce equivalent series
resistance and leakage current. Because it is generally intended to
improve the degree of edge coverage rather to impregnate the
interior of the anode body, the particles used in the external
coating typically have a larger size than those employed in the
solid electrolyte. For example, the ratio of the average size of
the particles employed in the external polymer coating to the
average size of the particles employed in any dispersion of the
solid electrolyte is typically from about 1.5 to about 30, in some
embodiments from about 2 to about 20, and in some embodiments, from
about 5 to about 15. For example, the particles employed in the
dispersion of the external coating may have an average size of from
about 80 to about 500 nanometers, in some embodiments from about 90
to about 250 nanometers, and in some embodiments, from about 100 to
about 200 nanometers.
[0069] If desired, a crosslinking agent may also be employed in the
external polymer coating to enhance the degree of adhesion to the
solid electrolyte. Typically, the crosslinking agent is applied
prior to application of the dispersion used in the external
coating. Suitable crosslinking agents are described, for instance,
in U.S. Patent Publication No. 2007/0064376 to Merker, et al. and
include, for instance, amines (e.g., diamines, triamines, oligomer
amines, polyamines, etc.); polyvalent metal cations, such as salts
or compounds of Mg, Al, Ca, Fe, Cr, Mn, Ba, Ti, Co, Ni, Cu, Ru, Ce
or Zn, phosphonium compounds, sulfonium compounds, etc.
Particularly suitable examples include, for instance,
1,4-diaminocyclohexane, 1,4-bis(amino-methyl)cyclohexane,
ethylenediamine, 1,6-hexanediamine, 1,7-heptanediamine,
1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine,
1,12-dodecanediamine, N, N-dimethylethylenediamine,
N,N,N',N'-tetramethylethylenediamine,
N,N,N',N'-tetramethyl-1,4-butanediamine, etc., as well as mixtures
thereof.
[0070] The crosslinking agent is typically applied from a solution
or dispersion whose pH is from 1 to 10, in some embodiments from 2
to 7, in some embodiments, from 3 to 6, as determined at 25.degree.
C. Acidic compounds may be employed to help achieve the desired pH
level. Examples of solvents or dispersants for the crosslinking
agent include water or organic solvents, such as alcohols, ketones,
carboxylic esters, etc. The crosslinking agent may be applied to
the capacitor body by any known process, such as spin-coating,
impregnation, casting, dropwise application, spray application,
vapor deposition, sputtering, sublimation, knife-coating, painting,
or printing, for example inkjet, screen or pad printing. Once
applied, the crosslinking agent may be dried prior to application
of the polymer dispersion. This process may then be repeated until
the desired thickness is achieved. For example, the total thickness
of the entire external polymer coating, including the crosslinking
agent and dispersion layers, may range from about 1 to about 50
.mu.m, in some embodiments from about 2 to about 40 .mu.m, and in
some embodiments, from about 5 to about 20 .mu.m.
[0071] E. Cathode Coating
[0072] If desired, the capacitor element may also employ a cathode
coating that overlies the solid electrolyte and other optional
layers (e.g., external polymer coating). The cathode coating may
contain a metal particle layer includes a plurality of conductive
metal particles dispersed within a polymer matrix. The particles
typically constitute from about 50 wt. % to about 99 wt. %, in some
embodiments from about 60 wt. % to about 98 wt. %, and in some
embodiments, from about 70 wt. % to about 95 wt. % of the layer,
while the polymer matrix typically constitutes from about 1 wt. %
to about 50 wt. %, in some embodiments from about 2 wt. % to about
40 wt. %, and in some embodiments, from about 5 wt. % to about 30
wt. % of the layer.
[0073] The conductive metal particles may be formed from a variety
of different metals, such as copper, nickel, silver, nickel, zinc,
tin, lead, copper, aluminum, molybdenum, titanium, iron, zirconium,
magnesium, etc., as well as alloys thereof. Silver is a
particularly suitable conductive metal for use in the layer. The
metal particles often have a relatively small size, such as an
average size of from about 0.01 to about 50 micrometers, in some
embodiments from about 0.1 to about 40 micrometers, and in some
embodiments, from about 1 to about 30 micrometers. Typically, only
one metal particle layer is employed, although it should be
understood that multiple layers may be employed if so desired. The
total thickness of such layer(s) is typically within the range of
from about 1 .mu.m to about 500 .mu.m, in some embodiments from
about 5 .mu.m to about 200 .mu.m, and in some embodiments, from
about 10 .mu.m to about 100 .mu.m.
[0074] The polymer matrix typically includes a polymer, which may
be thermoplastic or thermosetting in nature. Typically, however,
the polymer is selected so that it can act as a barrier to
electromigration of silver ions, and also so that it contains a
relatively small amount of polar groups to minimize the degree of
water adsorption in the cathode coating. In this regard, the
present inventors have found that vinyl acetal polymers are
particularly suitable for this purpose, such as polyvinyl butyral,
polyvinyl formal, etc. Polyvinyl butyral, for instance, may be
formed by reacting polyvinyl alcohol with an aldehyde (e.g.,
butyraldehyde). Because this reaction is not typically complete,
polyvinyl butyral will generally have a residual hydroxyl content.
By minimizing this content, however, the polymer can possess a
lesser degree of strong polar groups, which would otherwise result
in a high degree of moisture adsorption and result in silver ion
migration. For instance, the residual hydroxyl content in polyvinyl
acetal may be about 35 mol. % or less, in some embodiments about 30
mol. % or less, and in some embodiments, from about 10 mol. % to
about 25 mol. %. One commercially available example of such a
polymer is available from Sekisui Chemical Co., Ltd. under the
designation "BH-S" (polyvinyl butyral).
[0075] To form the cathode coating, a conductive paste is typically
applied to the capacitor that overlies the solid electrolyte. One
or more organic solvents are generally employed in the paste. A
variety of different organic solvents may generally be employed,
such as glycols (e.g., propylene glycol, butylene glycol,
triethylene glycol, hexylene glycol, polyethylene glycols,
ethoxydiglycol, and dipropyleneglycol); glycol ethers (e.g., methyl
glycol ether, ethyl glycol ether, and isopropyl glycol ether);
ethers (e.g., diethyl ether and tetrahydrofuran); alcohols (e.g.,
benzyl alcohol, methanol, ethanol, n-propanol, iso-propanol, and
butanol); triglycerides; ketones (e.g., acetone, methyl ethyl
ketone, and methyl isobutyl ketone); esters (e.g., ethyl acetate,
butyl acetate, diethylene glycol ether acetate, and methoxypropyl
acetate); amides (e.g., dimethylformamide, dimethylacetamide,
dimethylcaprylic/capric fatty acid amide and N-alkylpyrrolidones);
nitriles (e.g., acetonitrile, propionitrile, butyronitrile and
benzonitrile); sulfoxides or sulfones (e.g., dimethyl sulfoxide
(DMSO) and sulfolane); etc., as well as mixtures thereof. The
organic solvent(s) typically constitute from about 10 wt. % to
about 70 wt. %, in some embodiments from about 20 wt. % to about 65
wt. %, and in some embodiments, from about 30 wt. % to about 60 wt.
%. of the paste. Typically, the metal particles constitute from
about 10 wt. % to about 60 wt. %, in some embodiments from about 20
wt. % to about 45 wt. %, and in some embodiments, from about 25 wt.
% to about 40 wt. % of the paste, and the resinous matrix
constitutes from about 0.1 wt. % to about 20 wt. %, in some
embodiments from about 0.2 wt. % to about 10 wt. %, and in some
embodiments, from about 0.5 wt. % to about 8 wt. % of the
paste.
[0076] The paste may have a relatively low viscosity, allowing it
to be readily handled and applied to a capacitor element. The
viscosity may, for instance, range from about 50 to about 3,000
centipoise, in some embodiments from about 100 to about 2,000
centipoise, and in some embodiments, from about 200 to about 1,000
centipoise, such as measured with a Brookfield Dy-1 viscometer
(cone and plate) operating at a speed of 10 rpm and a temperature
of 25.degree. C. If desired, thickeners or other viscosity
modifiers may be employed in the paste to increase or decrease
viscosity. Further, the thickness of the applied paste may also be
relatively thin and still achieve the desired properties. For
example, the thickness of the paste may be from about 0.01 to about
50 micrometers, in some embodiments from about 0.5 to about 30
micrometers, and in some embodiments, from about 1 to about 25
micrometers. Once applied, the metal paste may be optionally dried
to remove certain components, such as the organic solvents. For
instance, drying may occur at a temperature of from about
20.degree. C. to about 150.degree. C., in some embodiments from
about 50.degree. C. to about 140.degree. C., and in some
embodiments, from about 80.degree. C. to about 130.degree. C.
[0077] F. Other Components
[0078] If desired, the capacitor may also contain other layers as
is known in the art.
[0079] In certain embodiments, for instance, a carbon layer (e.g.,
graphite) may be positioned between the solid electrolyte and the
silver layer that can help further limit contact of the silver
layer with the solid electrolyte. In addition, a pre-coat layer may
also be employed that overlies the dielectric and includes an
organometallic compound, such as described in more detail
below.
II. Terminations
[0080] Once the desired layers are formed, the capacitor may be
provided with terminations as indicated above. More particularly,
the capacitor contains an anode termination to which an anode lead
of the capacitor element is electrically connected and a cathode
termination to which the solid electrolyte of the capacitor element
is electrically connected. Any conductive material may be employed
to form the terminations, such as a conductive metal (e.g., copper,
nickel, silver, nickel, zinc, tin, palladium, lead, copper,
aluminum, molybdenum, titanium, iron, zirconium, magnesium, and
alloys thereof). Particularly suitable conductive metals include,
for instance, copper, copper alloys (e.g., copper-zirconium,
copper-magnesium, copper-zinc, or copper-iron), nickel, and nickel
alloys (e.g., nickel-iron). The thickness of the terminations is
generally selected to minimize the thickness of the capacitor. For
instance, the thickness of the terminations may range from about
0.05 to about 1 millimeter, in some embodiments from about 0.05 to
about 0.5 millimeters, and from about 0.07 to about 0.2
millimeters. One exemplary conductive material is a copper-iron
alloy metal plate available from Wieland (Germany). If desired, the
surface of the terminations may be electroplated with nickel,
silver, gold, tin, etc. as is known in the art to ensure that the
final part is mountable to the circuit board. In one particular
embodiment, both surfaces of the terminations are plated with
nickel and silver flashes, respectively, while the mounting surface
is also plated with a tin solder layer.
[0081] The terminations may be connected to the capacitor element
using any technique known in the art. In one embodiment, for
example, a lead frame may be provided that defines the cathode
termination and anode termination. To attach the capacitor element
to the lead frame, a conductive adhesive may initially be applied
to a surface of the cathode termination. The conductive adhesive
may include, for instance, conductive metal particles contained
with a resin composition. The metal particles may be silver,
copper, gold, platinum, nickel, zinc, bismuth, etc. The resin
composition may include a thermoset resin (e.g., epoxy resin),
curing agent (e.g., acid anhydride), and coupling agent (e.g.,
silane coupling agents). Suitable conductive adhesives may be
described in U.S. Patent Application Publication No. 2006/0038304
to Osako, et al. Any of a variety of techniques may be used to
apply the conductive adhesive to the cathode termination. Printing
techniques, for instance, may be employed due to their practical
and cost-saving benefits. The anode lead may also be electrically
connected to the anode termination using any technique known in the
art, such as mechanical welding, laser welding, conductive
adhesives, etc. Upon electrically connecting the anode lead to the
anode termination, the conductive adhesive may then be cured to
ensure that the electrolytic capacitor is adequately adhered to the
cathode termination.
[0082] Referring to FIG. 1, for example, a capacitor 30 is shown as
including an anode termination 62 and a cathode termination 72 in
electrical connection with a capacitor element 33 having an upper
surface 37, lower surface 39, front surface 36, rear surface 38,
first side surface 35, and opposing side surface (not shown). The
cathode termination 72 may be provided in electrical contact with
any surface of the capacitor element, such as via a conductive
adhesive. In the illustrated embodiment, for example, the cathode
termination 72 contains a first component 73 that is generally
parallel and adjacent to the upper surface 37 and a second
component 75 that is generally parallel and adjacent to the lower
surface 39. The first component 73 is also in electrical contact
with the upper surface 37. The cathode termination 72 may also
contain a third component 77 generally extends in a direction
perpendicular to the first component 73 and second component 75. If
desired, the third component 77 may also be provided in electrical
contact with the rear surface 38 of the capacitor element 33. The
anode termination 62 likewise contains a first component 63 that is
generally parallel to the lower surface 39 of the capacitor element
33 and a second component 67 that is generally parallel to the
anode lead 16. Further, the anode termination 62 may include a
third component 64 that is generally perpendicular to the first
component 63 and a fourth component 69 that is generally
perpendicular to the second component 67 and located adjacent to
the anode lead 16. In the illustrated embodiment, the second
component 67 and fourth component 69 define a region 51 for
connection to the anode lead 16. Although not depicted in FIG. 1,
the region 51 may possess a "U-shape" to further enhance surface
contact and mechanical stability of the lead 16.
[0083] The terminations may be connected to the capacitor element
using any technique known in the art. In one embodiment, for
example, a lead frame may be provided that defines the cathode
termination 72 and anode termination 62. To attach the capacitor
element 33 to the lead frame, a conductive adhesive 49 may
initially be applied to a surface of the cathode termination 72. In
one embodiment, the anode termination 62 and cathode termination 72
are folded into the position shown in FIG. 1. Thereafter, the
capacitor element 33 is positioned on the cathode termination 72 so
that its lower surface 39 contacts the adhesive 49 and the anode
lead 16 contacts the region 51. The anode lead 16 is then
electrically connected to the region 51 using any technique known
in the art, such as mechanical welding, laser welding, conductive
adhesives, etc. For example, the anode lead 16 may be welded to the
anode termination 62 using a laser. Lasers generally contain
resonators that include a laser medium capable of releasing photons
by stimulated emission and an energy source that excites the
elements of the laser medium. One type of suitable laser is one in
which the laser medium consist of an aluminum and yttrium garnet
(YAG), doped with neodymium (Nd). The excited particles are
neodymium ions Nd.sup.3+. The energy source may provide continuous
energy to the laser medium to emit a continuous laser beam or
energy discharges to emit a pulsed laser beam. Upon electrically
connecting the anode lead 16 to the anode termination 62, the
conductive adhesive may then be cured. For example, a heat press
may be used to apply heat and pressure to ensure that the
electrolytic capacitor element 33 is adequately adhered to the
cathode termination 72 by the adhesive 49. ps III. Barrier
Coating
[0084] As indicated above, a barrier coating is disposed on at
least a portion of the capacitor element and is in contact with the
casing material. One or multiple coatings may be employed. For
example, the coating may contact at least a portion of a surface of
the capacitor element, such as a front surface, bottom surface,
and/or top surface of the capacitor element. Optionally, the
barrier coating may also be disposed on at least a portion of the
anode termination and/or cathode termination. In one embodiment,
for instance, a barrier coating may be employed that covers at
least a portion of the anode termination. Likewise, the coating may
also contact at least a portion of the anode lead. In another
embodiment, a barrier coating may be employed that covers at least
a portion of the cathode termination. In such embodiments, the
coating may also contact at least a portion of a surface of the
capacitor element, such as a rear surface, top surface, and/or
bottom surface. Referring again to FIG. 1, for example, the
capacitor 30 is shown with a barrier coating 90 that is on the
anode termination 62. More particularly, in the illustrated
embodiment, the coating 90 is in contact with the second component
67 and the fourth component 69 of the anode termination 62 so that
the region 51 is generally covered. The coating 90 is also in
contact with at least a portion of the anode lead 16, particularly
at those locations surrounding the region 51 at which the lead 16
is connected to the anode termination 62. Of course, it should be
understood that the coating may also be provided in other
configurations and disposed on any surface desired. In one
embodiment, for example, the coating may contact only the second
component 67 of the anode termination 62.
[0085] Regardless of its location, the barrier coating may be
formed by applying a coating formulation to the part using a
variety of known techniques, such as by spin coating, impregnation,
pouring, dropwise application, injection, spraying, doctor blading,
brushing, printing (e.g., ink-jet, screen, or pad printing), or
dipping. Once applied, the coating formulation may be dried,
heated, and/or cured to remove any remaining solvent(s) and leave a
coating of the polymeric material at the desired location.
IV. Casing Material
[0086] As indicated, the capacitor element and anode lead are
generally encapsulated with a casing material so that at least a
portion of the anode and cathode terminations are exposed for
mounting onto a circuit board. Referring again to FIG. 1, for
instance, the capacitor element 33 and anode lead 16 may be
encapsulated within a casing material 28 so that a portion of the
anode termination 62 and a portion of the cathode termination 72
remain exposed. Further, as noted above, at least a portion of the
casing material 28 is also in contact with the barrier coating
90.
[0087] The casing material may be formed from a wide variety of
materials. In one embodiment, for instance, the casing material may
be formed from a curable resinous matrix, which may be hydrophobic.
In certain embodiments, for example, the resinous matrix may
contain a polycyanate containing at least two cyanate ester groups.
When cured, for example, the polycyanate may form a polycyanurate
having a triazine ring. Due to the high degree of symmetry in the
triazine ring, where dipoles associated with the carbon-nitrogen
and carbon-oxygen bonds are counterbalanced, the resulting
polycyanurate can have a relatively high degree of moisture
resistance. Suitable polycyanates may include, for instance,
bisphenol A dicyanate; the dicyanates of 4,4'-dihydroxydiphenyl,
4,4'-dihydroxydiphenyl oxide, resorcinyl, hydroquinone,
4,4'-thiodiphenol, 4,4'-sulfonyldiphenyl,
3,3',5,5'-tetrabromobisphenol A, 2,2',6,6'-tetrabromobisphenol A,
2,2'-dihydroxydiphenyl, 3,3'-dimethoxybisphenol A,
4,4'-dihydroxydiphenylcarbonate, dicyclopentadiene diphenol,
4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane,
tricyclopentadiene diphenol, etc.; the tricyanate of
tris(hydroxyphenyl)methane, the tetracyanate of
2,2',4,4'-tetrahydroxydiphenyl methane, the polycyanate of a
phenolformaldehyde condensation product (novolac); the polycyanate
of a dicyclopentadiene and phenol condensation product; and so
forth. If desired, the polycyanate may also contain one or more
polycyclic aliphatic radicals containing two or more cyclic rings,
such as a C.sub.7-C.sub.20 polycyclic aliphatic radical, including
cyclopentadiene, norbornane, bornane, norbornadiene,
trahydroindene, methyltetrahydroindene, dicyclopentadiene,
bicyclo-(2,2,l)-hepta-2,5-diene, 5-methylene-2-norbornene,
5-ethylidene-2-norbornene, 5-propenyl-2- norbornene,
5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene,
5-vinyl-2-norbornene, etc. In one particular embodiment, for
instance, the polycyanate may be a dicyclopentadiene bisphenol
cyanate ester. Without intending to be limited by theory, it is
believed such polycyclic radicals can act as a nonpolar bridging
group for the polycyanate, which helps improve moisture
resistance.
[0088] The resinous matrix may also contain an epoxy resin, either
alone or in combination with a polycyanate. When used in
combination, the epoxy resin can react with the polycyanate to form
a copolymer and/or crosslink with the polycyanate resin when cured.
Examples of suitable epoxy resins include, for instance, bisphenol
A type epoxy resins, bisphenol F type epoxy resins, phenol novolac
type epoxy resins, orthocresol novolac type epoxy resins,
brominated epoxy resins and biphenyl type epoxy resins, cyclic
aliphatic epoxy resins, glycidyl ester type epoxy resins,
glycidylamine type epoxy resins, cresol novolac type epoxy resins,
naphthalene type epoxy resins, phenol aralkyl type epoxy resins,
cyclopentadiene type epoxy resins, heterocyclic epoxy resins, etc.
To help provide the desired degree of moisture resistance, however,
it is particularly desirable to employ epoxy phenol novolac ("EPN")
resins, which are glycidyl ethers of phenolic novolac resins. These
resins can be prepared, for example, by reaction of phenols with an
excess of formaldehyde in the presence of an acidic catalyst to
produce the phenolic novolac resin. Novolac epoxy resins are then
prepared by reacting the phenolic novolac resin with
epichlorihydrin in the presence of sodium hydroxide. Specific
examples of the novolac-type epoxy resins include a phenol-novolac
epoxy resin, cresol-novolac epoxy resin, naphthol-novolac epoxy
resin, naphthol-phenol co-condensation novolac epoxy resin,
naphthol-cresol co-condensation novolac epoxy resin, brominated
phenol-novolac epoxy resin, etc. Regardless of the type of resin
selected, the resulting phenolic novolac epoxy resins typically
have more than two oxirane groups and can be used to produce cured
coating compositions with a high crosslinking density, which can be
particularly suitable for enhancing moisture resistance. One such
phenolic novolac epoxy resin is poly[(phenyl glycidyl
ether)-co-formaldehyde]. Other suitable resins are commercially
available under the trade designation ARALDITE (e.g., GY289, EPN
1183, EP 1179, EPN 1139, and EPN 1138) from Huntsman.
[0089] The polycyanate and/or epoxy resin may be crosslinked with a
co-reactant (hardener) to further improve the mechanical properties
of the composition and also enhance its overall moisture resistance
as noted above. Examples of such co-reactants may include, for
instance, polyamides, amidoamines (e.g., aromatic amidoamines such
as aminobenzamides, aminobenzanilides, and
aminobenzenesulfonamides), aromatic diamines (e.g.,
diaminodiphenylmethane, diaminodiphenylsulfone, etc.),
aminobenzoates (e.g., trimethylene glycol di-p-aminobenzoate and
neopentyl glycol di-p-amino-benzoate), aliphatic amines (e.g.,
triethylenetetramine, isophoronediamine), cycloaliphatic amines
(e.g., isophorone diamine), imidazole derivatives, guanidines
(e.g., tetramethylguanidine), carboxylic acid anhydrides (e.g.,
methylhexahydrophthalic anhydride), carboxylic acid hydrazides
(e.g., adipic acid hydrazide), phenolic-novolac resins (e.g.,
phenol novolac, cresol novolac, etc.), carboxylic acid amides,
etc., as well as combinations thereof. Phenolic-novolac resins may
be particularly suitable for use in the present invention.
[0090] The casing material may also contain an inorganic oxide
filler. Such fillers are typically maintained at a high level of
the casing material, such as from about 75 wt. % to about 99.5 wt.
%, in some embodiments from about 76 wt. % to about 99 wt. %, and
in some embodiments, from about 77 wt. % to about 90 wt. % of the
casing material, while the resinous matrix typically constitutes
from about 0.5 wt. %
[0091] to about 25 wt. %, in some embodiments from about 1 wt. % to
about 24 wt. %, and in some embodiments, from about 10 wt. % to
about 23 wt. % of the casing material. The nature of the inorganic
oxide fillers may vary, such as silica, alumina, zirconia,
magnesium oxides, iron oxides (e.g., iron hydroxide oxide yellow),
titanium oxides (e.g., titanium dioxide), zinc oxides (e.g., boron
zinc hydroxide oxide), copper oxides, zeolites, silicates, clays
(e.g., smectite clay), etc., as well as composites (e.g.,
alumina-coated silica particles) and mixtures thereof. Regardless
of the particular fillers employed, however, a substantial portion,
if not all, of the inorganic oxide fillers is typically in the form
of vitreous silica, which is believed to further improve the
resistance of the casing material to thermal expansion due to its
high purity and relatively simple chemical form. Vitreous silica
may, for instance, constitute about 30 wt. % or more, in some
embodiments from about 35 wt. % to about 90 wt. %, and in some
embodiments, from about 40 wt. % to about 80 wt. % of the total
weight of fillers employed in the composition, as well as from
about 20 wt. % to about 70 wt. %, in some embodiments from about 25
wt. % to about 65 wt. %, and in some embodiments, from about 30 wt.
% to about 60 wt. % of the entire composition. Of course, other
forms of silica may also be employed in combination with the
vitreous silica, such as quartz, fumed silica, cristabolite,
etc.
[0092] Apart from the components noted above, it should be
understood that still other additives may also be employed in the
casing material, such as photoinitiators, viscosity modifiers,
suspension aiding agents, pigments, stress reducing agents,
coupling agents (e.g., silane coupling agents), stabilizers, etc.
When employed, such additives typically constitute from about 0.1
to about 20 wt. % of the total composition.
[0093] The particular manner in which the casing material is
applied to the capacitor element may vary as desired. In one
particular embodiment, the capacitor element is placed in a mold
and the casing material is applied to the capacitor element so that
it occupies the spaces defined by the mold and leaves exposed at
least a portion of the anode and cathode terminations. The casing
material may be initially provided in the form of a single or
multiple compositions. For instance, a first composition may
contain the resinous matrix and filler and the second composition
may contain a co-reactant. Regardless, once it is applied, the
casing material may be heated or allowed to stand at ambient
temperatures so that the resinous matrix is allowed to crosslink
with the co-reactant, which thereby causes the casing material to
cure and harden into the desired shape of the case. For instance,
the casing material may be heated to a temperature of from about
15.degree. C. to about 150.degree. C., in some embodiments from
about 20.degree. C. to about 120.degree. C., and in some
embodiments, from about 25.degree. C. to about 100.degree. C.
[0094] The present invention may be better understood by reference
to the following examples.
Test Procedures
Capacitance
[0095] The capacitance may be measured using a Keithley 3330
Precision LCZ meter with Kelvin Leads with 2.2 volt DC bias and a
0.5 volt peak to peak sinusoidal signal. The operating frequency
may be 120 Hz and the temperature may be 23.degree. C..+-.2.degree.
C. In some cases, the "wet-to-dry" capacitance can be determined.
The "dry capacitance" refers to the capacitance of the part before
application of the solid electrolyte, graphite, and silver layers,
while the "wet capacitance" refers to the capacitance of the part
after formation of the dielectric, measured in 14% nitric acid in
reference to 1 mF tantalum cathode with 10 volt DC bias and a 0.5
volt peak to peak sinusoidal signal after 30 seconds of electrolyte
soaking.
Equivalent Series Resistance (ESR)
[0096] Equivalence series resistance may be measured using a
Keithley 3330 Precision LCZ meter with Kelvin Leads 2.2 volt DC
bias and a 0.5 volt peak to peak sinusoidal signal. The operating
frequency may be 100 kHz and the temperature may be 23.degree.
C..+-.2.degree. C.
Dissipation Factor
[0097] The dissipation factor may be measured using a Keithley 3330
Precision LCZ meter with Kelvin Leads with 2.2 volt DC bias and a
0.5 volt peak to peak sinusoidal signal. The operating frequency
may be 120 Hz and the temperature may be 23.degree. C..+-.2.degree.
C.
Leakage Current
[0098] Leakage current may be measured using a leakage test meter
at a temperature of 23.degree. C..+-.2.degree. C. and at the rated
voltage after a minimum of 60 seconds.
Load Humidity Testing
[0099] Humidity testing may be based on standard IEC 68-2-67:1995
(85.degree. C./85% relative humidity). 25 test parts (mounted on a
printed circuit board substrate) may be loaded with rated voltage
at the aforementioned humidity test conditions. Capacitance and ESR
may be measured at 0, 120, 250, 500, 1000 and 1500 hours at a
temperature of 23.degree. C..+-.2.degree. C. after 2 to 24 hours
from recovery of the humidity test conditions.
High Temperature Storage Testing
[0100] High temperature storage testing may be based on IEC
60068-2-2:2007 (condition Bb, temperature 150.degree. C.). 25 test
parts (not mounted on a printed circuit board substrate) may be
tested at the aforementioned temperature conditions. All
measurements of capacitance and ESR may be conducted at a
temperature of 23.degree. C..+-.2.degree. C. after 1 to 2 hours
from recovery of the temperature test conditions.
Sensitivity Level (MSL) Testing
[0101] MSL may be tested according to IPC/JEDEC J-STD 020E
(December 2014) to Level 4 and 3 with reflow for Pb-free assembly.
Reflow peak temperature (Tp) may be 260.degree. C. Visual
evaluation of cracks may be measured with 40 times
magnification.
Example 1
[0102] 40,000 .mu.FV/g tantalum powder was used to form anode
samples. Each anode sample was embedded with a tantalum wire,
pressed to a density of 5.3 g/cm3 and sintered at 1380.degree. C.
The resulting pellets had a size of 5.20.times.3.60.times.0.75 mm.
The pellets were anodized to 75.0 volts in water/phosphoric acid
electrolyte with a conductivity of 8.6 mS at a temperature of
40.degree. C. to form the dielectric layer. The pellets were
anodized again to 130 volts in a water/boric acid/disodium
tetraborate with a conductivity of 2.0 mS at a temperature of
30.degree. C. for 10 seconds to form a thicker oxide layer built up
on the outside. Upon anodization, four pre-coat layers of
organometallic compound were used that contained a solution of
(3-aminopropyl)trimethoxysilane in ethanol (1.0%). A conductive
polymer coating was formed by dipping the anodes into a solution of
poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butane-sulpho-
nic acid having a solids content of 2.0% (Clevios.TM. K, Heraeus).
Upon coating, the parts were dried at 125.degree. C. for 15
minutes. This process was repeated 2 times. Thereafter, the parts
were dipped into a dispersed poly(3,4-ethylenedioxythiophene)
having a solids content 1.1% and viscosity 20 mPas (Clevios.TM. K,
Heraeus). Upon coating, the parts were dried at 125.degree. C. for
15 minutes. This process was repeated 8 times. Thereafter, the
parts were dipped into a dispersed poly(3,4-ethylenedioxythiophene)
having a solids content 2.0% and viscosity 20 mPas (Clevios.TM. K,
Heraeus). Upon coating, the parts were dried at 125.degree. C. for
15 minutes. This process was repeated 3 times. Thereafter, the
parts were dipped into a dispersed poly(3,4-ethylenedioxythiophene)
having a solids content of 2% and viscosity 160 mPas (Clevios.TM.
K, Heraeus). Upon coating, the parts were dried at 125.degree. C.
for 15 minutes. This process was repeated 14 times. The parts were
then dipped into a graphite dispersion and dried. Finally, the
parts were dipped into a silver dispersion and dried. Multiple
parts (950) of 47pF/35V capacitors were made in this manner and
encapsulated in a silica resin.
Example 2
[0103] Capacitors were formed in the manner described in Example 1,
except that capacitor elements were coated by a polymeric material
as described above prior to encapsulation. Multiple parts (3300) of
47pF/35V capacitors were made in this manner and encapsulated in a
silica resin.
[0104] Moisture sensitivity level was tested for each sample after
96 hours (MSL4) and 192 hours (MSL3) according to IPC/JEDEC J-STD
020E (December 2014). The ratio of the cracked parts is set forth
below in Table 1. The sample size was 100 units minimum for each
humidification time.
TABLE-US-00002 TABLE 1 MSL Testing - Failed Parts Ratio Crack Fail
Ratio (%) 96 hrs 30.degree. C./60% RH 192 hrs 30.degree. C./60% RH
Example 1 22 26 Example 2 0 2
[0105] These and other modifications and variations of the present
invention may be practiced by those of ordinary skill in the art,
without departing from the spirit and scope of the present
invention. In addition, it should be understood that aspects of the
various embodiments may be interchanged both in whole or in part.
Furthermore, those of ordinary skill in the art will appreciate
that the foregoing description is by way of example only, and is
not intended to limit the invention so further described in such
appended claims.
* * * * *